• Title/Summary/Keyword: chlorinated aliphatic

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Development and Application of an In Situ Technology to Treat Various Soil and Groundwater Contaminants

  • Goltz, Mark N.
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2003.10a
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    • pp.89-110
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    • 2003
  • The limitations of conventional soil and groundwater contamination remediation technologies have motivated a search for innovative technologies; particularly in situ technologies that do not require extraction of contaminants from the subsurface. All engineered in situ remediation systems require that the contaminant be mixed with a remedial compound. Horizontal flow treatment wells (HFTWs), an innovative technology that consists of a pair of dual-screened treatment wells, were used at a trichloroethylene (TCE) contaminated site to efficiently achieve this mixing of contaminant and remedial compound in order to effect in situ bioremediation (McCarty et al., 1998). In this paper, the potential of HFTWs to treat chlorinated aliphatic hydrocarbons (CAHs) as well as other soil and groundwater contaminants of concern, such as nitroaromatic compounds (NACs), perchlorate, and methyl-tert-butyl ether (MTBE), is examined. Through a combination of laboratory studies, model analyses, and field evaluations, the effectiveness of this innovative technology to manage these contaminants is investigated.

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Field Studios of In-situ Aerobic Cometabolism of Chlorinated Aliphatic Hydrocarbons

  • Semprini, Lewts
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2004.04a
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    • pp.3-4
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    • 2004
  • Results will be presented from two field studies that evaluated the in-situ treatment of chlorinated aliphatic hydrocarbons (CAHs) using aerobic cometabolism. In the first study, a cometabolic air sparging (CAS) demonstration was conducted at McClellan Air Force Base (AFB), California, to treat chlorinated aliphatic hydrocarbons (CAHs) in groundwater using propane as the cometabolic substrate. A propane-biostimulated zone was sparged with a propane/air mixture and a control zone was sparged with air alone. Propane-utilizers were effectively stimulated in the saturated zone with repeated intermediate sparging of propane and air. Propane delivery, however, was not uniform, with propane mainly observed in down-gradient observation wells. Trichloroethene (TCE), cis-1, 2-dichloroethene (c-DCE), and dissolved oxygen (DO) concentration levels decreased in proportion with propane usage, with c-DCE decreasing more rapidly than TCE. The more rapid removal of c-DCE indicated biotransformation and not just physical removal by stripping. Propane utilization rates and rates of CAH removal slowed after three to four months of repeated propane additions, which coincided with tile depletion of nitrogen (as nitrate). Ammonia was then added to the propane/air mixture as a nitrogen source. After a six-month period between propane additions, rapid propane-utilization was observed. Nitrate was present due to groundwater flow into the treatment zone and/or by the oxidation of tile previously injected ammonia. In the propane-stimulated zone, c-DCE concentrations decreased below tile detection limit (1 $\mu$g/L), and TCE concentrations ranged from less than 5 $\mu$g/L to 30 $\mu$g/L, representing removals of 90 to 97%. In the air sparged control zone, TCE was removed at only two monitoring locations nearest the sparge-well, to concentrations of 15 $\mu$g/L and 60 $\mu$g/L. The responses indicate that stripping as well as biological treatment were responsible for the removal of contaminants in the biostimulated zone, with biostimulation enhancing removals to lower contaminant levels. As part of that study bacterial population shifts that occurred in the groundwater during CAS and air sparging control were evaluated by length heterogeneity polymerase chain reaction (LH-PCR) fragment analysis. The results showed that an organism(5) that had a fragment size of 385 base pairs (385 bp) was positively correlated with propane removal rates. The 385 bp fragment consisted of up to 83% of the total fragments in the analysis when propane removal rates peaked. A 16S rRNA clone library made from the bacteria sampled in propane sparged groundwater included clones of a TM7 division bacterium that had a 385bp LH-PCR fragment; no other bacterial species with this fragment size were detected. Both propane removal rates and the 385bp LH-PCR fragment decreased as nitrate levels in the groundwater decreased. In the second study the potential for bioaugmentation of a butane culture was evaluated in a series of field tests conducted at the Moffett Field Air Station in California. A butane-utilizing mixed culture that was effective in transforming 1, 1-dichloroethene (1, 1-DCE), 1, 1, 1-trichloroethane (1, 1, 1-TCA), and 1, 1-dichloroethane (1, 1-DCA) was added to the saturated zone at the test site. This mixture of contaminants was evaluated since they are often present as together as the result of 1, 1, 1-TCA contamination and the abiotic and biotic transformation of 1, 1, 1-TCA to 1, 1-DCE and 1, 1-DCA. Model simulations were performed prior to the initiation of the field study. The simulations were performed with a transport code that included processes for in-situ cometabolism, including microbial growth and decay, substrate and oxygen utilization, and the cometabolism of dual contaminants (1, 1-DCE and 1, 1, 1-TCA). Based on the results of detailed kinetic studies with the culture, cometabolic transformation kinetics were incorporated that butane mixed-inhibition on 1, 1-DCE and 1, 1, 1-TCA transformation, and competitive inhibition of 1, 1-DCE and 1, 1, 1-TCA on butane utilization. A transformation capacity term was also included in the model formation that results in cell loss due to contaminant transformation. Parameters for the model simulations were determined independently in kinetic studies with the butane-utilizing culture and through batch microcosm tests with groundwater and aquifer solids from the field test zone with the butane-utilizing culture added. In microcosm tests, the model simulated well the repetitive utilization of butane and cometabolism of 1.1, 1-TCA and 1, 1-DCE, as well as the transformation of 1, 1-DCE as it was repeatedly transformed at increased aqueous concentrations. Model simulations were then performed under the transport conditions of the field test to explore the effects of the bioaugmentation dose and the response of the system to tile biostimulation with alternating pulses of dissolved butane and oxygen in the presence of 1, 1-DCE (50 $\mu$g/L) and 1, 1, 1-TCA (250 $\mu$g/L). A uniform aquifer bioaugmentation dose of 0.5 mg/L of cells resulted in complete utilization of the butane 2-meters downgradient of the injection well within 200-hrs of bioaugmentation and butane addition. 1, 1-DCE was much more rapidly transformed than 1, 1, 1-TCA, and efficient 1, 1, 1-TCA removal occurred only after 1, 1-DCE and butane were decreased in concentration. The simulations demonstrated the strong inhibition of both 1, 1-DCE and butane on 1, 1, 1-TCA transformation, and the more rapid 1, 1-DCE transformation kinetics. Results of tile field demonstration indicated that bioaugmentation was successfully implemented; however it was difficult to maintain effective treatment for long periods of time (50 days or more). The demonstration showed that the bioaugmented experimental leg effectively transformed 1, 1-DCE and 1, 1-DCA, and was somewhat effective in transforming 1, 1, 1-TCA. The indigenous experimental leg treated in the same way as the bioaugmented leg was much less effective in treating the contaminant mixture. The best operating performance was achieved in the bioaugmented leg with about over 90%, 80%, 60 % removal for 1, 1-DCE, 1, 1-DCA, and 1, 1, 1-TCA, respectively. Molecular methods were used to track and enumerate the bioaugmented culture in the test zone. Real Time PCR analysis was used to on enumerate the bioaugmented culture. The results show higher numbers of the bioaugmented microorganisms were present in the treatment zone groundwater when the contaminants were being effective transformed. A decrease in these numbers was associated with a reduction in treatment performance. The results of the field tests indicated that although bioaugmentation can be successfully implemented, competition for the growth substrate (butane) by the indigenous microorganisms likely lead to the decrease in long-term performance.

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Concentrations of VOCs in Groundwater Associated with Land Uses in Ulsan Area (토지이용에 따른 울산지역 지하수의 VOCs 함량 특성)

  • Yun Uk;Cho Byong-Wook
    • Economic and Environmental Geology
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    • v.37 no.6 s.169
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    • pp.613-629
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    • 2004
  • Contamination of groundwater by volatile organic compounds (VOCs) was investigated for 168 groundwater wells in Ulsan area to study the natural attenuation of organic compounds in the aquifers. As groundwater contamination by VOCs is closely related to land use, 168 groundwater samples were classified into 4 different groups; agricultural, forestry, industrial, and residential & business. From analysis 65 out of 168 groundwater samples contained more than one VOC. Analysis of samples were performed fir 36 halogenated aliphatic hydrocarbons and 25 petroleum hydrocarbons set up by NAWQA of US geological survey. Twelve petroleum hydrocarbons were detected in 26 groundwater wells, but their concentrations were less than 1.5 g/L except for MTBE. Twenty three chlorinated aliphatic hydrocarbons, composed of 11 methanes, 6 ethanes and 6 ethenes, were detected in 63 groundwater samples. The range of methanes concentration was $ND\~330\;/gL,\;ethanes\;ND\~84\;gL$, and PCE and their derivatives $ND\~62\;g/L$. As the study area was comprised of the aerobic/denitrification zones and $Fe^{+3}$ redox condition, most of petroleum hydrocarbons were degraded well, while halogenated hydrocarbons were slowly biodegradation.

Prediction of $EC_{50}$ of Photobacterium phosphoreum for CAHs and Chlorophenol Derivatives Using QSAR (QSAR방법을 이용한 CAHs와 Chlorophenol 유도체에 대한 $EC_{50}$값 예측)

  • Lee, Hong-Joo;Yoo, Seung-O;Lee, Jeong-Gun;Kim, Byung-Yong;Chun, Uck-Han
    • Microbiology and Biotechnology Letters
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    • v.27 no.1
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    • pp.54-61
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    • 1999
  • Measurement of inhibition of bioluminescence in Photobacterium phosphoreum has been porposed as a sensitive and rapid procedure to monitor toxic substances. However, at first, $EC_{50}$ which shows degree of toxicity to each toxic substances must be calculated. QSAR (Quantitative Structure Activity Relationship) model can be used to estimate $EC_{50}$ to save time and endeavor. Moderately high correlation coefficients ($r^2{\geq}$ 0.97) were calculated from the linear correlation between $EC_{50}$ and molecular connectivity indices of CAHs (chlorinated aliphatic hydrocarbons)such as $^0X$, $^0X^V$, $^1X$, $^2X$ and $^3X^v_c$ and quadratic correlation between $EC_{50}$ and $^0X$, $^0X^V$, $^2X^V$, $^3X_c$, $^3X^V_c$ and P. It shows that the molecular connection indices in carbon structure is contributed to biological characters with linear relation and that in the other one with quadratic relation. The $EC_{50}$ of chlorophenol derivatives had quadratic relation with the value of octanol/water prtition coefficients ($r^2$=0.99) and linear and quadratic relation with the number of chlorine compound (($r^2{\geq}$0.94). This confirms the already known trend of increasing toxicity with increasing ability of a compound to diffuse through cell membrane and number of chlorine substitution.

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Characterization of Atmospheric Concentrations of Volatile Organic Compounds in Industrial Areas of Pohang and Gumi Cities (포항과 구미의 대규모 산단지역 대기 중 휘발성 유기화합물 농도 분포 특성에 관한 연구)

  • Baek Sung-Ok;Kim Soo-Hyun;Kim Mi-Hyun
    • Environmental Analysis Health and Toxicology
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    • v.20 no.2 s.49
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    • pp.167-178
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    • 2005
  • This study was carried out to evaluate the temporal, spatial, and seasonal variations of VOC, and to characterize the VOC concentrations in two large industrial complexes located in Pohang and Gumi cities. Twenty -four hours continuous sampling of selected VOC was made with STS 25 sequential tube samplers and double-bed adsorbent tubes. Air samples were collected every three hour interval for 7 consecutive days in each site during summer and winter. VOC were determined by thermal desorption coupled with GC/MS. A total of 27 VOCs of environmental concern were determined, including aliphatic, aromatic and halides. Generally. concentrations of toxic VOC were higher in Gumi than Pohang, and VOC levels in industrial areas were typically several-fold higher than those in residential areas. The most abundant VOC appeared to be toluene for both cities. However, chlorinated VOC were higher in Gumi than Pohang, while aromatic VOC were more abundant in Pohang than in Gumi. Two cities showed relatively different variations of VOC concentrations within a day. It is likely that traffic related sources are major factors affecting the VOC in Pohang, and industrial solvents usages are important sources in Gumi. These results imply that the occurrence and levels of atmospheric VOC are strongly dependent on the type of industries in each city. Therefore, in order to develop any control strategies or to establish the priority rankings for VOC in large industrial complexes, the type of industries and the occurrence of VOC in the atmosphere should be taken into consideration.

CAH degradation characteristics under mixed conditions (혼합조건에서의 CAH 화합물 분해 특성에 관한 연구)

  • 김종호;배우근;심호재;신언빈
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2001.04a
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    • pp.214-217
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    • 2001
  • 자연계에서는 오염물질이 단일물질로 존재하기보다는 혼합물로 존재하는 것이 대부분이다. 본 연구에서는 지하수 오염물질 chlorinated aliphatic hydrocarbon(CAH)들 중 trichloroethylene(TCE), vinyl chloride(VC)에 대해서 Fe$^{\circ}$와 함께 미생물, 활성탄을 이용하여 단일물질 및 혼합물질상태에서 그 분해특성을 살펴보았다. 실험은 120$m\ell$ serum bottle을 이용하여 단일물질 및 혼합물질상태에서 그 분해특성을 살펴보았다. 실험은 120$m\ell$ serum bottle을 이용하였고 headspace 50${\mu}\ell$를 GC에 주입하여 각 오염물질 농도를 분석하였으며, Fe$^{\circ}$, Fe$^{\circ}$+ cell, Fe$^{\circ}$+ 활성탄 3가지 조건에서 TCE (25${\mu}\ell$)가 단일화합물 또는 VC(10$\mu\textrm{m}$)와 혼합화학물로 존재시 분해특성을 조사하였다. 단일화합물로 존재시 2시간후 TCE농도 측정 결과 Fe$^{\circ}$만을 이용하였을 때보다 활성탄, Cell을 함께 이용하였을 경우 그 분해율이 각각 1.6배, 1.8배 높게 나타났다. 그러나, VC와 혼화합물로 존재시 TCE 분해율은 단일 화합물로 존재시와 비교 Fe$^{\circ}$, Fe$^{\circ}$+ 활성탄, Fe$^{\circ}$+ cell 조건에서 각각 63%, 28%, 5%로 나타났다. VC는 Fe$^{\circ}$만으로는 분해가 되지 않았지만 cell에 의해 완전분해 되었으며, 함께 존재시 TC는 Fe$^{\circ}$만으로는 분해가 되지 않았지만 cell에 의해 완전분해 되었으며, 함께 존재시 TCE분해에 저해작용을 미치는 것으로 나타났다.

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Purification and Characterization of a Tetrachloroethylene (PCE) Dehalogenase from Clostridium bifermentans DPH-1 (C. bifermentans DPH-1 균주로부터 정제한 테트라클로로에틸렌 (PCE) 분해효소의 제성질)

  • Chang, Young-Cheol;Jeong, Kweon;Yoo, Young-Sik;Kim, Min-Young;Shin, Jae-Young
    • Journal of Environmental Health Sciences
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    • v.26 no.2
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    • pp.14-21
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    • 2000
  • DEAE-Toyopearl 650S, Superdex pg-75, Poros HQ, Superdex H200의 각종 칼러크로마토그래피를 이용하여 C.bifermentans DPH-1균주로부터 테트라클로로에틸렌(PCE) 분해 효소를 정제했다. 이 PCE 분해효소 (PCE dehalogenase)는 PCE를 환원적 탈염소화 반응에 의해 시스디클로로에딜렌 (cis-1,2-dichloroethylene)에 전환 가능하여, 이 때의 Vmax 및 Km 치는 각각 73 nmol/h.mg protein, 12$\mu$M이었다. 본 PCE dehalogenase의 겔여과 분자량 Maker Kit를 이용한 분석결과(70kDa)는 SDS-PAGE에 나타난 분자량(35kDa)의 약 2배인 것으로 확인되었다. 따라서 본 효소는 분자량 70kDa의 이량체(Homo dimer)인 것으로 추정되었다. 본 효소의 최적온도 및 pH는 각각 35$^{\circ}C$ 및 8.0 이었다. 또한 본 효소는 PCE외의 트리클로로에틸렌, 디클로로에틸렌 이성체, 1,2-디클로로에템, 1,2-디클로로프로판, 1,1,2-트리클로로에탄에 대하여도 활성을 타나내었다. N-말단 아미노산 분석결과에서도 본 효소는 현재 알려진 PCE dehalogenase와 그 배열이 전혀 다른 것으로 나타나 각종 유기염소 화합물의 분해능을 보유한 신종의 PCE 분해효소인 것이 확인되었다.

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Screening of Zero-Valent Metal for the Removal of High Concentration PCE and 1,1,1 TCA (고농도 PCE 및 1,1,1 TCA 제거를 위한 영가금속 선정)

  • Kwon, Soo-Youl;Kim, Young
    • Journal of Wetlands Research
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    • v.12 no.1
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    • pp.23-31
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    • 2010
  • Chlorinated aliphatic hydrocarbons (CAHs) such as tetrachloroethylene (PCE), 1,1,1-trichloroethane (1,1,1-TCA) are the contaminants most frequently found in soil and groundwater. They have a potential to be toxic to and persistent in environment. This study is focused on selection of zero-valent metal and ores for the removal of high concentration PCE or 1,1,1-TCA and mixture of two compound. For the screening of suitable metals, we measured dechlorination rate, removal capacities and economics by using batch reactor test. This results suggest that removal rate and dechlorination of high quality iron and zinc are higher than slag and nature ores like zinc and manganese. Among nature ores, zinc ores(64% purity) have highest removal capacities. And in economics zinc ores is 10 times better than high quality metal tested. We conclude zinc ore is most suitable metal for the removal of PCE or 1,1,1-TCA.

Characteristics of Groundwater, Sewage Water and Stream Water Contamination Based on VOCs Concentration Around Ulsan, Korea (울산지역 지하수, 하수 및 하천수의 VOCs 오염특성)

  • Cho, Byong-Wook;Yun, Uk;Im, Hyun-Chul;Sung, Ig-Hwan;Jang, Woo-Seog
    • Economic and Environmental Geology
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    • v.38 no.1
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    • pp.57-65
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    • 2005
  • To investigate the characteristics of the volatile organic compounds (VOCs) concentration in the groundwater around Ulsan, Korea, 168 groundwaters, 12 stream waters, and 6 sewage waters were analyzed for 61 VOCs. Results showed that VOCs were not detected in stream waters and total VOCs concentration in 5 sewage waters was in the range of ND-22.3 ${\mu}$g/L. In 78 groundwater samples more than one VOCs were detected and VOCs concentration of the samples ranged from 0.1 ${\mu}$g/L to 387.1 ${\mu}$g/L. However, VOCs concentration of 66 samples out of 78 samples showed less than 10 ${\mu}$g/L and that of only 6 samples exceeded Korea drinking water limit (KDWL). 42 VOCs detected from the 168 groundwaters were 14 aromatic hydrocarbons out of 25, 27 chlorinated aliphatic hydrocarbons out of 35, and methyl tert-butyl ether (MTBE). Detection rate of each VOCs in the groundwaters was as follows: chloroform in 43 samples (25.6%), methylene chloride in 36 samples (21.4%), TCE in 26 samples (15.5%), 1,1-dichloroethane in 19 samples (1.3%), PCE in 16 samples (9.5%), cis-1,2-DCE in 15 samples (8.9%), and toluene in 14 samples (8.3%). Even though VOCs concentration in the groundwaters of the study area is still low, the city is expanding and the drinking water limit is becoming strict, and therefore continuous monitoring is necessary.

Transformation Characteristics of Chlorinated Aliphatic Hydrocarbon (CAH) Mixtures by Natural Ores (자연광석을 이용한 염소계 지방족 탄화수소 혼합물 변환 특성)

  • Son, Bong-han;Kim, Nam-hee;Hong, Kwang-pyo;Yun, Jun-ki;Lee, Chae-young;Kim, Young;Kwon, Soo-youl
    • Journal of Korean Society on Water Environment
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    • v.23 no.5
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    • pp.712-722
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    • 2007
  • This study screened three natural ores (iron, mangenase, and zinc), two types of slags, and two elemental metals (elemental iron and zinc) to evaluate transformation characteristics of CAH mixtures [e.g. Carbontetrachloride (CT), 1,1,1-Trichloroethane (1,1,1-TCA), and Perchloroethene (PCE)]. To select an effective metal medium to treat the CAH mixtures, we measured transformation capacities (CAH mass ultimately transformed/mass of metal added) and the degree of dechlorination. We also considered economical efficiency of the metal media by comparing the value, CAH mass ultimately transformed divided by the price of metal medium added. A simplified mathematical model adapting CAH transformation capacity, first-order transformation kinetics, and available mass of metal transforming CAH was developed and used for estimating CAH transformation rate coefficient and longevity of the metal medium. CAH transformation capacity for elemental iron and elemental zinc were 4258~7129 and $4215{\sim}6330{\mu}g\;CAH\;transformed/g$ metal added, respectively, which are a factor of 80~200 higher than slags and natural ores. They also showed a factor of 1.1 to 2.2 greater degree of dechlorination than the others. Among natural ores and slags, Zinc ore showed the highest transformation capacity, $47{\sim}53{\mu}g\;CAH\;transformed/g$ metal added. Although zinc ore have smaller transformation capacity than elemental metals, economical efficiency of zinc ore is a factor of 10~20 greater than elemental metals tested. Consequently, zinc ore would be more economical medium than the others tested in this study. We estimated the pseudo first-order transformation rate of zinc ore was in the order of CT > 1,1,1-TCA > PCE.